Production of dyestuff



Patented Mar. 29, 1949 2,465,883

UNITED STATES PATENT OFFICE PRODUCTION OF DYESTUFF IN TERMEDIATES John David Kendall and Frank Peter Doyle, Ilford, England, assignors to Ilford Limited, Ilford, England, a British company No Drawing. Application July 1, 1946, Serial No. 680,824. In Great Britain July 3, 1945 6 Claims. (01. 2e0-240) 1 2 This invention relates to dyestufi intermediates. r In co-pending U. S. application Serial No.

scribed for the production of compounds of the X general formula as follows: l

---D--. --o---, RI ---DI---- chain of three methylene groups any of which 0 I may be hydrocarbon-substituted. Such com- Whlch 1s tautomeric pounds may be defined as A -[3-alkyl (or T (2) aralkyl) thio] cyclohexenone (1-) compounds. ('JOCHr-C=CC=(CHCH),.=N

The monothio ether compounds of the above R2 X Formula 1 are made as described in the above ap- I plication by reacting a cyclic 1,3-diketone of the and reaction (B) appears to proceed as Shown m general formula the following equation:

D -r"" I"'- ""1 l p! (50 cH-t': SR on 00 N"--R (50CH2-C=O f 2- 3 wherein D has the same significance as in the l (3) Formula 1 with an alkyl, aryl, or aralkyl mercaptan (RSH) in the presence of a strong acid, "I e. g., dry hydrochloric acid, nitric acid, sulphuric I I acid, phosphoric acid, or strong organic acids, OFCILFOEFCOFNFR e. g., p-toluene sulphonic acid. which is tautomelic with In carrying out the reaction one molecular equivalent of the cyclic ketone is treated with i I (l; I

preferably not less than two molecular equiva- (IQ-CHM): C O, N R3 lents of mercaptan; a considerable excess of mer In these formulae R and D have the meanings captain y be present and function as a solvent. assigned to them above, D1 is the residue of a The quantity of the strong acid is not critical, but five-membered or six-membered heterocyclic generally at least one molecular equivalent of a nitrogen nucleus, D2 is the residue of a fivedibasic acid or at least two molecular equivalents b d h ter eyeli nitrogen-keto-methylene of a o obas c acid ay b employed. I nucleus, R1 is hydrogen or a hydrocarbon group,

It it preferred to keep the reaction mixture. as R is an alkyl r aralkyl group, R3 is hydrogen or y as p s A o n or t e eac may a hydrocarbon group,"X is an acid radicle and n be present, e. g., benzene, toluene or a lower alis nought or one.

h or a t for ampl di thyl ether. As indicated above the reactions are efiected e IeaCtiOH proceeds at normal room tempe by heating the reagents together. In case (A) ture and there is no necessity to heat the reaction where a quaternary salt is used, it is unnecessary mixture. to isolate the quaternary salt and, in fact, a pre- According to this invention dyestuff inters ferred procedure is to react together the heteromediates are Produced by ea n a ompound of cyclic nitrogen base, suificient of an alkyl or general Formula 1 with (A) an alkyl or aralkyl -25 aralkyl salt to convert the base to the quaternary quaternary salt of a five-membered or six-memsalt, and the compound of Formula 1.

bered heterocyclic nitrogen compound contain- The reaction (A) may be applied to all types of ing a reactive methylene group in the ea or 'y pofive-membered and six-membered heterocyclic sition to the quaternary nitrogen atom, or (B) nitrogen nuclei. Thus D1 may be the residue of with a five-membered heterocyclic nitrogenasubstituted or unsubstituted thiazolathiazoline, keto-methylene compound, in the presence of a oxazole, oxazoline, selenazole, selenazoline, pyrinon-basic compound which will combine with dine, quinoline, lepidine, indolenine, diazine (e. g. the mercaptan RSH eliminated in the reaction. pyrimidine), thiodiazole or quinazoline, or of a Reaction (A) appears to proceed as shown in corresponding polycyclic compound such as a the following equation: 5:; benzthiazole or naphthathiazole.

The reaction (B) may be applied to all fivemembered heterocyclic nitrogen-keto-methylene compounds: examples are rhodanic acid, oxarhodanic acid (and their N-hydrocarbon substituted analogues), oxindoles, pyrazole--ones, hydantoin, pseudohydantoin, thiohydantoin and pseudothiohydantoin.

The group R is preferably a lower alkyl group, e. g. methyl or ethyl, as this makes for greater ease of reaction. The group R1, if not a hydrogen atom, is preferably a lower alkyl group, though it may be a higher alkyl or aralkyl or aryl group. The group R2 may be any alkyl or aralkyl group, e. g. methyl, ethyl, propyl or benzyl, and the group R3 may be any of these alkyl or aralkyl groups or an aryl group, e. .g. phenyl or naphthyl. Such alkyl, aralkyl and aryl groups may themselves be substituted; for example R2 may be a fi-hydroxyethyl group.

The residue D may be the simple grouping CH2CH2CH2- or may be any corresponding grouping in which one or more of the hydrogen atoms are substituted by hydrocarbon groups, e. g. methyl, ethyl, propyl, isopropyl, styryl or phenyl.

Typical A -(3-alkylthio) cyclohexenone (1) compounds which may be employed are:

A -(3-ethylthio-5 2:5 dimethyl) (1) A -(3-ethylthio-5-phenyl) cyc'lohexenone (1') A'-= -(3-ethy1thio-5 methyl) cyc'lohexenone (1) A -(3-ethy1thio) cyclohexenone (1') and analogous compounds produced by the method of the aforesaid application Serial No. 680,822 from 5-isopropyl-cyclohexane dione :3)

4:5 :5-trimethyl-cyclohexane dione (l :3) 4-phenyl-5 5-dimethyl-cyelohexane dione (1:3) 5-styryl-cyclohexane dione (1:3)

cyclohexenone Example 1 Preparation of the intermediate shown in the following formula:

'1 parts of A -('3-ethylthio-5t5 dimethyl) cyclohexenone (1), 3.7 parts of l-methyl benzthiazole and 4.7 parts of methyl-'p-toluene sulphonat'e were fused together at 100 C. for 2 hours. 150 parts of acetic anhydride were then added and the mixture refluxed for 1 hour when a deep orange colour had formed. The excess acetic anhydride was removed in vacuo, the residue dissolved in ethyl alcohol and poured into aqueous potassium iodide solution, from which, on cooling, the dyestuff intermediate crystallised. This was removed by filtration and washed with ethyl alcohol and water. It was an orange solid, M. Pt. 191 C.

Example 2 Preparation of the intermediate shown in the following formula:

C-CH=C C=O (5) Ha CH C H SO CH 1 7 x 3 egg \CH3 5.96 parts of l-methyl benzthiazole, 7.44 parts of methyl-p-toluene sulphonate and 7.36 parts of A -(3 ethylthio 5:5'dimethyl) cyclohexenone (l) were fused at 130-140" for 3 hours. 40 parts of acetic anhydride were added and the whole refiuxed for 1 hour. The excess acetic anhydride was evaporated in vacuo and the residue washed with ether and water and then made to crystallise by treatment with acetone and ether. After recrystallisation from ethyl alcohol the product was obtained as an orange solid, M. Pt. C.

Example 3 Preparation of the intermediate shown in the following formula:

Example 4 Preparation of the intermediate shown in the following formula:

This was prepared as in Example 2 using the following quantities: '7 .5 parts of l-methyl benzthiazole, 10 parts of ethyl-p-toluene sulphonate and 10 parts of A -(3-ethylthio-5:5'dimethyl) cyclohexenone (l). The mixture was fused at 160* for 4 hours, 150 parts of acetic anhydride were then added and the mixture boiled as before. The product was an oran e solid. M. Pt. 127 C Example 5 Preparation of the intermediate shown in the following formula:

.0 e g CH;

Example 6 Preparation of the intermediate shown in the following formula:

10 parts of A -(3-ethylthio-5:Sdimethyl) cyclohexenone (l), 7.9 parts of p-toluquinaldine, 10 parts of ethyl-p-toluene sulphonate, and 150 parts of acetic anhydride were reacted exactly as in Example 5. The product Was a dark orange solid, M. Pt. 210 0.

Example 7 Preparation of the intermediate shown in the following formula:

o (12H; I l on3 1.49parts of l-methyl benzthiazole and 2 parts of ethyl-p-toluene sulphonate were fused for 3 hours at 140-150". 1.7 parts of A -(3-ethylthio- 5-methyl) cyclohexenone (1) were added and the mixture re-fused for 2 hours at 160. 20 parts of acetic anhydride were then added and the mixture refluxed for 1 hour. The product was isolated and purified as in the previous examples. It was an orange solid, M. Pt. 211 C. (with decomposition) Example 8 Preparation of the intermediate shown in the following formula:

on! 3 SO3C1H7 1.5 parts of l-methyl benzthiazole, 1.9 parts of methyl-p-toluene sulphonate and 1.6 parts of A -(3-ethylthio)-cyclohexenone (l) were fused together at 140-150 for 3 hours. parts of acetic anhydride were added and the whole boiled for 1 hours. The product was isolated as in Example 2 as a light orange solid, M. Pt. 112 C.

Example 9 Preparation of the intermediate shown in the following formula:

3.0 gms. of N-metliyl rhodanic acid'and 3.7 gms. of A -(3-ethylthio-5:S'dimethyl) cyclohexenone (1) were fused at 120-l30 C. for 2 hours and then boiled for 1 hour with cc. of acetic anhydride. The excess acetic anhydride was evaporated in vacuo and the residue dissolved in a little ethyl alcohol from which, on cooling, the intermediate crystallised. It was removed by filtration and recrystallised from ethyl alcohol when it was obtained as red crystals, M. Pt. 192 C.

Example 10 Preparation of the intermediate shown in the following formula:

3.5 gms. of 1-phenyl-3-methyl-5-pyrazolone and 3.7 gms. of A -(3-ethy1thio-5:5'dimethy1) cyclohexenone (1) were fused at 130-140 C. for 4 hours and then boiled with 25 cc. of acetic anhydride. The intermediate was isolated as in Example 2, recrystallised from ethyl alcohol and further purified by extraction with ether, the intermediate being obtained by evaporation of the ether solution. It was ayellow solid, M. Pt. 110 o. c

Many of the dye intermediates produced according to this invention may be condensed as described in co-pending U. S. application Serial No. 680,825 filed July 1', 1 946.

What we claim is;

1. Process for the production of dyestufi intermediates which comprises heating a compound of the general formula:

where R is selected from the class consisting of alkyl and aralkyl groups and D is a chain of three methylene groups any of which may be hydrocarbon-substituted, with a compound selected from the class consisting of alkyl and aralkyl quaternary salts of five-membered and six-membered heterocyclic nitrogen compounds containing a reactive methylene group in one of the positions alpha and gamma to the quaternary nitrogen atom and five-membered heteorcyclic nitrogen keto-methylene compounds, the reaction being effected in the presence of a non-basic compound which will combine with the mercaptan (RSH) eliminated in the reaction.

2. Process for the production of dyestuif intermediates which comprises heating a compound of the general formula:

where R is selected from the class consisting of alkyl and aralkyl groups and D is a chain of three methylene groups any of which may be hydrocarbon-substituted, with a compound selected from the class consisting of alkyl and aralkyl quaternary salts of five-membered and six-membered heterocyclic nitrogen compounds containing a reactive methylene group in one of the positions alpha and gamma to the quaternary nitrogen atom and five-membered heterocyclic nitrogen keto-methylene compounds, the reaction 7 being effected in the presence of an acid an hydride.

3. Process for theproduction of dyestuff intermediates which comprises heating a compound of the general formula:

('Jo-oH=& sn where R is selected from the class consistingof alkyl and aralkyl groups and D is a chain of three methylene groups any of which may be hydrocarbon-substituted, with a compound selected from the class consisting of five-membered and six-membered heterocyclic nitrogen bases containing a reactive methylene group in one of the positions alpha and gamma to the heterocyclic nitrogen atom and with suflicient of a compound selected from the class consisting of alkyl and aralkyl salts to convert the said base to the corresponding quaternary salt, the said reaction being effected in the presence of a non-basic compound which will combine with the mercaptan (RSI-I) eliminated in the reaction.

4. Process for the production of dyestuff intermediates which comprises heating a compound of the general formula:

oo-on=o-sa where R is selected from the class consisting of alkyl and aralkyl groups and D is a chain of three methylene groups any of which may be hydrocarbon-substituted, with a compound selected fromthe class consisting of five-membered and SiX -memb81ed heterocyclic nitrogen bases containing a reactive methylene group in one of the positions alpha and gamma to the heterocyclic nitrogen atom and with suificient of a compound selected from the class consisting of alkyl and 8 aralkyl salts to convert the said base to the corresponding quaternary salt, the said reaction being effected in the presence of an acid anhydride.

5. Dyestufi intermediates of the general forwhere R1 is selected from the class consisting of hydrogen and hydrocarbon groups, R2 is selected from the class consisting of alkyl and aralkyl groups, D is a chain of three methylene groups any of which may be hydrocarbon-substituted, D1 is a residue selected from the residues of fivemembered and six-membered heterocyclic nitrogen nuclei, X is an acid radicle and n is selected from nought and one.

6. Dyestuff intermediates of the general for mula:

l --1 1-1 oo-oH,-('1=oc o-N-R: where D is a chain of three methylene groups any of which may be hydrocarbon-substituted, D2 is the residue of a heterocyclic nitrogen ketomethylene nucleus and R3 is selected from the class consisting of the hydrogen atom and hydrocarbon groups.

JOHN DAVID KENDALL; FRANK PETER DOYLE.

REFERENCES CITED The following references are of record in the 

